ES2837119T3 - Antifouling coating composition - Google Patents

Abstract

Resin composition, configured to comprise a polymer (A), and at least one component selected from acidic compounds, basic compounds and compounds that can react with an acid, in which the polymer (A) comprises at least one derived structural unit of a monomer having the structure represented by the following formula (1), (2) or (3), and in which, after storage of the resin composition at 40 ° C for 30 days, the decomposition rate of the structure represented by the formula (1), (2) or (3) in the polymer (A) is 20% or less, the decomposition rate of the structure represented by the formula (1), (2) or ( 3) is defined as: (decomposition rate) = {(measured solid acid number (a)) - (theoretical solid acid number (b))} / (theoretical solid acid number (c)) × 100 (index of theoretical solid acid) = Σ (561 * 100 / Mwi * wi) where, "wi" represents the mass fraction of the monomer that contains an acid functional group (i) of a copolymer (A), and "Mwi" indicates the molecular weight of the monomer containing an acid functional group, the monomer containing an acid functional group (i) occurs when the structure represented by the formula (1), (2) or (3) decomposes, and the measured solid acid number (a) is performed according to the following procedure: in a beaker, about 4.0 grams of a sample (A (g)) is weighed, in which 50 ml of a solution containing toluene and 95% ethanol in a 50/50 ratio are added, the mixture is placed in an airtight container and stirred for 5 minutes, using a Hiranuma automatic titrator (AutoTitrator COM-1600) To perform potentiometric titration with a 0.5 mol / L potassium hydroxide solution (ethanol solution), with a factor (f) of 1.003 at 20 ° C, the end point is set at the maximum slope point of the titration curve (titration volume = B (ml), KOH solution titer = f), is carried out or the same procedure on a blank sample (titration volume = C (ml)), and the acid number is calculated by the following equation, solid acid number (mgKOH / g) = {(BC) × 0.5 × 56.11 × f} / A / solid component, ** (See formula) ** in which, in the above formulas, "X" represents an ether oxygen atom, a sulfur sulfur atom or a sulfur atom amine nitrogen; R1 and R2 each represent a hydrogen atom or a C1 to C10 alkyl group; R3 and R5 each represent a C1 to C20 alkyl, cycloalkyl or aryl group; and R4 and R6 each represent a C1 to C10 alkylene group.

Description

DESCRIPTION

Antifouling coating composition

Technical field

The present invention relates to an antifouling coating composition.

This application is based on Japanese Patent Applications No. 2015-084199, filed April 16, 2015, No. 2015-175470, filed September 7, 2015, and No. 2015-177629, filed 9 September 2015, of which he claims priority.

Background

It is known to apply antifouling coating paints on marine structures such as ships (particularly the underside of a ship) in order to prevent the adhesion of underwater organisms that can cause corrosion of the submerged part or decrease in the speed of navigation. Hydrolyzable antifouling coating paints are widely used due to their characteristics. The surface of the coating film formed by a hydrolyzable antifouling coating paint gradually dissolves in water to be renewed (self-polishing), and the antifouling component is constantly exposed on the surface of the coating, thus showing long-lasting antifouling effects. As hydrolyzable antifouling paints, antifouling coating paints using metal-containing polymers are known. For example, patent documents 1 and 2 propose coating compositions formed using divalent metal-containing resins. However, as described in ^patent documents 1 ^and 2 ^{, when cuprous oxide generally used as an antifouling agent is added to achieve} excellent long-lasting antifouling effects in seawater, the dissolution stability of the coating composition tends decrease. Therefore, problems such as decreased self-polishing properties caused by a decrease in the hydrolysis rate (also known as dissolution rate) of the coating film can arise.

Patent document 3 proposes a hydrolyzable coating composition formed mainly using a resin containing a 1- (alkyloxy) ester group as a non-metallic resin. When a coating paint includes a non-metallic resin as the main component, its long-term dissolving ability will not decrease. However, the coating film formed by the coating composition of patent document 3 shows low dissolution stability and its hydrolysis rate (also known as dissolution rate) increases with time. Consequently, an excessive amount of coating film is consumed, making it difficult to obtain long-lasting coating effects. Furthermore, as the dissolution rate increases chronologically, the water resistance of the coating film decreases and defects such as cracking and peeling are likely to occur.

Furthermore, as a solvent for reducing viscosity and improving coating ability, the coating composition proposed in patent document 3 has a higher content of a volatile organic compound (hereinafter abbreviated as "VOC"), which needs to be reduced by in view of environmental concerns. As described, insufficient dissolution stability of conventional coating films causes problems such as lower self-polishing properties due to reduced dissolution rates, excessive consumption of coating films due to increased dissolution rates, etc. Therefore, long-lasting antifouling effects cannot be expected from conventional coating films. Other problems are lower storage stability and higher VOC content.

List of citations

Patent documents

Patent Document 1: JP 2002-12630A

Patent Document 2: JP H07-64985B

Patent Document 3: JP H04-103671A

Other relevant documents are documents EP-A-1367100, US-A-2012/010342 and US-A-2009/053366.

Summary of the invention

Problems to be solved by the invention

The object of the present invention is to provide a resin composition for producing a low ^c O ^v antifouling coating composition having excellent storage stability and coating ability, such that said antifouling coating composition can form a film of coating that exhibits high dissolution stability and self-polishing properties while avoiding excessive film consumption and flaws to achieve long-lasting antifouling effects.

Solutions to problems

The present invention has the following aspects.

[1] A resin composition formed to comprise a polymer (A) containing at least one structural unit derived from a monomer having a structure represented by the following formula (1), (2) or (3) and wherein , after storage of the resin composition at 40 ° C for 30 days, the decomposition rate of the structure represented by formula (1), (2) or (3) in the polymer (A) is 20% or less

(In the above formulas, "X" represents an ether oxygen atom, a sulfur sulfur atom, or an amine nitrogen atom; R1 and R2 each represent a hydrogen atom or a C1 to C10 alkyl group; R3 and R5 each represent a C1 to C20 alkyl, cycloalkyl or aryl group, which may be substituted with at least one substituent selected from cycloalkyl, aryl, alkoxy, alkanoyloxy and aralkyl groups; and R4 and R6 each represent a C1 alkylene group to C10, which may be substituted with at least one substituent selected from cycloalkyl, aryl, alkoxy, alkanoyloxy and aralkyl groups)

and containing at least one component selected from compounds that can react with an acid, acidic compounds and basic compounds.

[3] The resin composition according to [2], wherein the acid-reactive compound includes at least one compound represented by the following formula (31), (32) or (33).

(In the above formulas, "X" represents an ether oxygen atom, a sulfur sulfur atom, or an amine nitrogen atom; R7 represents a hydrogen atom or a C1 to C9 alkyl group; R8 represents a C1 to C9 alkyl group. hydrogen or a C10 alkyl group; R9 and R11 each represent a C1 to C20 alkyl, cycloalkyl or aryl group, which may be substituted with at least one substituent selected from cycloalkyl, aryl, alkoxy, alkanoyloxy and aralkyl groups; R10 represents a single bond or a C1 to C9 alkylene group, which may be substituted with at least one substituent selected from cycloalkyl, aryl, alkoxy, alkanoyloxy and aralkyl groups; and R12 represents a C1 to C9 alkylene group, which may be substituted with al less one substituent selected from cycloalkyl, aryl, alkoxy, alkanoyloxy and aralkyl groups).

[4] The resin composition according to any one of [1] to [3], wherein the polymer (A) includes a structural unit derived from a monomer having a structure represented by the following formula (1).

(In the above formula (1), "X" represents an ether oxygen atom, a sulfur sulfide atom or an amine nitrogen atom; R1 and R2 each represent a hydrogen atom or a C1 alkyl group to C10; R3 represents a C1 to C20 alkyl, cycloalkyl or aryl group, which may be substituted with at least one substituent selected from among cycloalkyl, aryl, alkoxy, alkanoyloxy and aralkyl groups; and the total number of carbon atoms in R1, R2 and R3 is 4 or more).

[5] The resin composition according to any one of [1] to [4], wherein the polymer (A) includes a structural unit derived from a monomer having a structure represented by the following formula (1).

(In the above formula (1), "X" represents an ether oxygen atom, a sulfur sulfide atom or an amine nitrogen atom; R1 and R2 each represent a hydrogen atom or a C1 alkyl group to C10; R3 represents a C1 to C20 alkyl, cycloalkyl or aryl group, which may be substituted with at least one substituent selected from among cycloalkyl, aryl, alkoxy, alkanoyloxy and aralkyl groups; and the total number of carbon atoms in R1, R2 and R3 is 8 or more).

[6] The resin composition according to any one of [1] to [5], wherein the polymer (A) further includes a structural unit derived from a (meth) acrylate monomer containing an oxyethylene group represented by the following formula (2-1).

Z1- (CH2CH2O) nR21 ■■■ (2-1)

(In the formula, Z1 represents an acryloyloxy or methacryloyloxy group; R21 represents a hydrogen atom or a C1 to C10 alkyl or aryl group; and "n" is an integer from 1 to 15).

[7] The resin composition according to any one of [1] to [6], in which the weight average molecular weight of the polymer (A) is 2,000 to 19,000, the content of the polymer (A) is at least 57% of the total mass of the resin composition, and the viscosity at 25 ° C determined using a Brookfield viscometer is less than 2,000 mPas.

[8] The resin composition according to any one of [1] to [7], wherein the weight average molecular weight of the polymer (A) is 3,000 to 16,000, the content of the polymer (A) is at least 59% of the total mass of the resin composition, and the viscosity determined as before is less than 1,000 mPas.

[9] An antifouling coating composition, formed to comprise the resin composition according to any one of [1] to [8] and an antifouling agent.

[10] The antifouling coating composition according to [9], which contains at least one antifouling agent selected from cuprous oxide, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3- carbonitrile and medetomidine.

[11] The antifouling coating composition according to [9] or [10], wherein the content of a volatile organic compound is 410 g / l or less.

[12] The antifouling coating composition according to any one of [9] to [11], wherein the viscosity at 25 ° C determined using a Brookfield viscometer is less than 3,000 mPas.

[13] The antifouling coating composition according to any one of [9] to [12], wherein after storage at 40 ° C for 90 days, the change in viscosity determined using a Brookfield viscometer is 400% or less .

[14] The antifouling coating composition according to any one of [9] to [13] further containing a thermoplastic resin.

Effects of the invention

In accordance with the present invention, there is provided a resin composition for producing a low VOC antifouling coating composition having excellent storage stability and coating ability, so that said antifouling coating composition can form a coating film which Exhibit high dissolution stability and self-polishing properties while avoiding excessive film consumption and flaws to achieve long-lasting antifouling effects.

Detailed description of the realizations

The following definitions of terms apply to the specification and claims herein invention.

A "volatile organic compound (VOC)" means an organic compound that readily volatilizes under normal conditions of temperature and pressure. Normal temperature and pressure mean 10 ° C to 30 ° C and 1000 Pa to 1050 Pa, for example.

A "structural unit" means a unit formed by polymerization of a monomer, or a unit in which a part is converted into a different structure by treatment of a polymer.

"(Met) acrylate" refers collectively to acrylate and methacrylate, and "(meth) acrylic acid" refers collectively to acrylic acid and methacrylic acid.

<Resin composition>

The resin composition of the present invention is formed to comprise a polymer (A) containing at least one structural unit derived from a monomer having a structure represented by the following formula (1), (2) or (3), and wherein, after storage of the resin composition at 40 ° C for 30 days, the decomposition rate of the structure represented by formula (1), (2) or (3) in the polymer (A) is 20% or less.

(In the above formulas, "X" represents an ether oxygen atom, a sulfur sulfur atom, or an amine nitrogen atom; R1 and R2 each represent a hydrogen atom or a C1 to C10 alkyl group; R3 and R5 each represent a C1 to C20 alkyl, cycloalkyl or aryl group, which may or may not be substituted with at least one substituent selected from cycloalkyl, aryl, alkoxy, alkanoyloxy and aralkyl groups; and R4 and R6 each represent a group C1 to C10 alkylene, which may or may not be substituted with at least one substituent selected from cycloalkyl, aryl, alkoxy, alkanoyloxy and aralkyl groups).

<(Co) polymer (A)>

The polymer (A) includes a structural unit derived from a monomer having the structure represented by the following formula (1), (2) or (3).

(In the above formulas, "X" represents an ether oxygen atom, a sulfur sulfur atom, or an amine nitrogen atom; R1 and R2 each represent a hydrogen atom or a C1 to C10 alkyl group; R3 and R5 each represent a C1 to C20 alkyl, cycloalkyl or aryl group, which may or may not be substituted with at least one substituent selected from cycloalkyl, aryl, alkoxy, alkanoyloxy and aralkyl groups; and R4 and R6 each represent a group C1 to C10 alkylene, which may or may not be substituted with at least one substituent selected from cycloalkyl, aryl, alkoxy, alkanoyloxy and aralkyl groups).

To improve the dissolution stability of the coating film, the monomer having the structure represented by formula (1) is most preferred.

In formula (1), when R1 or R2 is C1 to C10 alkyl group, examples of C1 to C10 alkyl group are methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl, 2-ethylhexyl group and the like.

When R1 or R2 is a C1 to C10 alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 4, more preferably 1 to 3, even more preferably 1 or 2.

Examples of a preferred combination of R1 and R2 are a hydrogen atom and a methyl group, two methyl groups, a hydrogen atom and a C2 to C10 alkyl group (hereinafter also referred to as "long chain alkyl group"), a methyl group and a long chain alkyl group, two hydrogen atoms, two long chain alkyl groups, and the like. Among them, to achieve a proper hydrolysis property of the coating film, a combination of a hydrogen atom and a methyl group is preferable.

When R3 is a C1 to C20 alkyl group, the aforementioned C1 to C10 alkyl groups, a decyl group, dodecyl group, tetradecyl group or the like may be represented by R3, for example. When R3 is a C1 to C20 alkyl group, the number of carbon atoms in R3 is preferably 3 to 20, more preferably 7 to 20. When the number of carbon atoms is 7 or more, excellent strength is obtained water and crack resistance.

When R3 is a cycloalkyl group, preferred examples are C4 to C8 cycloalkyl groups, such as a cyclohexyl or cyclopentyl group.

When R3 is an aryl group, preferred examples are C6 to C20 aryl groups, such as a phenyl or naphthyl group. As R3, a C3 to C20 alkyl or cycloalkyl group is preferred.

Furthermore, the total number of carbon atoms in R1, R2 and R3 is preferably 4 or more, more preferably 8 or more. By setting the total number in such a range, excellent water resistance and crack resistance are obtained.

The alkyl, cycloalkyl, or aryl groups in R3 may be substituted with at least one substituent selected from cycloalkyl, aryl, alkoxy, alkanoyloxy, and aralkyl groups. When substituted, the number of substituents can be one or more than one.

The cycloalkyl and aryl groups as substituents can be those listed above. Examples of the alkoxy group are a methoxy group, ethoxy group, propoxy group, butoxy group, and the like. Examples of the alkanoyloxy group are an ethanoyloxy group or the like. As the aralkyl group, a benzyl group or the like can be used.

In formula (2), when R4 is a C1 to C10 alkylene group, a methylene group, ethylene group, propylene group, butylene group, hexylene group or the like, for example, may be represented by R4

The number of carbon atoms in R4 is preferably 2 to 7, more preferably 3 to 4.

The alkylene group may be substituted with at least one substituent selected from cycloalkyl, aryl, alkoxy, alkanoyloxy, and aralkyl groups. When substituted, the number of substituted groups can be one or more than one. Specific examples of a substituent that may be substituted with an alkylene group are those listed as examples of R3.

In formula (3), the examples of R5 are the same as those of R3 in formula (1), and the preferred embodiment is also the same. On the other hand, the examples of R6 are the same as those of R4 in formula (2), and the preferred embodiment is also the same.

As the polymer (A), a polymer having the structural unit (u1) derived from a monomer (m1) having an ethylenically unsaturated bond (polymerizable carbon-carbon double bond) and a functional group (I) is preferable. The structural unit (u1) of polymer (A) can be of one type or of two or more types.

In addition to the structural unit (u1), the polymer (A) can also include another structural unit (u2) other than the structural unit (u1).

Preferably, the polymer (A) is a (meth) acrylic polymer from the viewpoint of hydrolysis properties, water resistance, resistance to cracking and storage stability. A "(meth) acrylic polymer" means a polymer in which at least a part of the structural unit of the polymer (A) is a unit derived from a (meth) acrylic monomer. Said (meth) acrylic polymer may further include a structural unit derived from a monomer other than the (meth) acrylic monomer (for example, a vinyl monomer such as styrene). A "(meth) acrylic monomer" means a monomer with an acryloyl group or a methacryloyl group. When the polymer (A) is a (meth) acrylic polymer having structural units (u1) and (u2), a structural unit derived from a (meth) acrylic monomer can be included in one or both of the structural units (u1) and ^(u 2 ^).

(Structural unit (u1))

The structural unit (u1) has a structure formed when an ethylenically unsaturated bond is cleaved from the ^{monomer (m} 1 ^).

Taking into account the viscosity of the resin composition, the monomer (m1) is preferably a monofunctional monomer having an ethylenically unsaturated bond.

Examples of monomer (m1) are compounds represented by the following formula (11), (12) or (13).

(In the above formulas, "X" represents an ether oxygen atom, a sulfur sulfide atom, or an ^{amine nitrogen atom; "Z" represents CH} 2 ^{= CH-COO-, CH (CH} 3 ^{) = CH -COO-, CH} 2 ^{= C (CH} 3 ^{) -COO-, CHRX = CH-COO-, CH} 2 ^{= C (CH} 2 ^{Rx) -COO-, or CH} 2 ^{= CRx-CH} 2 ^{COO-; Rx represents a 1- (alkyloxy) ester group, 1- (alkylthio) ester} group, 1- (dialkylamino) ester group or alkyl ester group; R1 and R2 each represent a hydrogen atom or a C1 to C10 alkyl group; R3 and R5 represent each a C1 to C20 alkyl, cycloalkyl or aryl group, which may or may not be substituted with at least one substituent selected from the cycloalkyl, aryl, alkoxy, alkanoyloxy and aralkyl groups; and R4 and R6 each represent a C1 alkylene group to C10, which may or may not be substituted with at least one substituent selected from the groups cycloalkyl, aryl, alkoxy, alkanoyloxy and aralkyl).

R1 to R6 in formulas (11) to (13) correspond respectively to R1 to R6 in formulas (1) to (3) mentioned above.

^{As indicated above for "Z", CH} 2 ^{= CH-COO- is an acryloyloxy group, and CH2 = C (CH3) -COO- is a} methacryloyloxy group. CH (CH3) = CH-COO- is a crotonoyloxy group (the ethylenically unsaturated bond is a trans isomer) or an isocrotonoyloxy group (the ethylenically unsaturated bond is a cis isomer). CHRX = CH-COO- is a maleinoyloxy group (the ethylenically unsaturated bond is a cis isomer) or a fumaroyloxy group (the ethylenically ^{unsaturated bond is a trans isomer), in which a carboxyl group is substituted with a} 1 ^{- (alkyloxy group ) ester,} 1- ^{(alkylthio) ester group,} 1- ^{(dialkylamino) ester group or alkyl ester group.}

When RX is a 1- (alkyloxy) ester group, 1- (alkylthio) ester group or 1- (dialkylamino) ester group, the examples of RX are the same as those listed above. Preferably, RX has the same structure as the group to ^{which "Z" is attached. For example, when a compound is represented by formula (} 11 ^{), preferably RX is} a group represented by -CR1R2-OR3.

When RX is an alkyl ester group, RX is represented by -COORX1, with RX1 being an alkyl group. ^{Preferably, the alkyl group for RX1 is a C1 to C6 alkyl group , especially preferably a methyl group.}

^CH 2 ^{= C (CH} 2 ^{Rx) -COO- or CH} 2 ^{= CRx-CH} 2 ^{COO- is an itaconoyloxy group in which a carboxyl group is substituted} with a 1 - (alkyloxy) ester group, 1 - (alkylthio) group ester, 1- (dialkylamino) ester group or alkyl ester group. RX is the same as those listed above.

^{Preferably, "Z" is CH} 2 ^{= CH-COO-, or CH (CH3) = CH-COO-.}

Examples of monomer (m1) are represented below.

(Structural unit (u2))

Examples of structural unit (u2) are structural units derived from a monomer (m2) that has an ethylenically unsaturated bond but does not have a functional group (I). Such a structural unit has the structure formed ^{when the ethylenically unsaturated bond of the monomer (m} 2 ^{) is cleaved.}

Examples of monomer (m2) are substituted or unsubstituted alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate , n-butyl ^{(meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate,} 2- ^{ethylhexyl (meth) acrylate, lauryl (meth) acrylate,} stearyl (meth) acrylate , Behenyl (meth) acrylate, 1-methyl-2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate and 3-methyl-3-methoxybutyl (meth) acrylate; substituted or unsubstituted aralkyl (meth) acrylates such as benzyl (meth) acrylate, m-methoxyphenylethyl (meth) acrylate and p-methoxyphenylethyl (meth) acrylate; substituted or unsubstituted aryl (meth) acrylates such as phenyl (meth) acrylate, m-methoxyphenyl (meth) acrylate, pmethoxyphenyl (meth) acrylate and o-methoxyphenylethyl (meth) acrylate; alicyclic (meth) acrylates such as isobornyl (meth) acrylate and cyclohexyl (meth) acrylate; (meth) acrylate monomers containing hydrophobic groups such as trifluoroethyl (meth) acrylate, perfluorooctyl (meth) acrylate and perfluorocyclohexyl (meth) acrylate; (meth) acrylate monomers ^{containing oxyethylene groups such as} 2- ^{methoxyethyl (meth) acrylate,} 2- ^{ethoxyethyl (meth) acrylate,} 2- ^{butoxyethyl (meth) acrylate, butoxidyethylene glycol (meth) acrylate, (meth) acrylate methoxytriethylene glycol, methoxypolyethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, and} 2- ⁽ 2- ^{ethylhexaoxy) ethyl (meth) acrylate; (meth) acrylate monomers containing hydroxyl groups such as} 2- ^{hydroxyethyl (meth) acrylate,} 2- ^{hydroxypropyl} (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerol (meth) acrylate; terminal alkoxyallylated polyether monomers such as methoxypolyethylene glycol allyl ether, methoxypropylene glycol allyl ether, butoxypolyethylene glycol allyl ether, butoxypolypropylene glycol allyl ether, methoxypolyethylene glycol allyl ether, butoxypropylene glycol polypropylene glycol ether; vinyl monomers containing epoxy groups such as glycidyl (meth) acrylate, glycidyl α-ethyl acrylate and 3,4-epoxybutyl (meth) acrylate; vinyl monomers containing primary or secondary amino groups such as butylaminoethyl (meth) acrylate and (meth) acrylamide; vinyl monomers containing tertiary amino groups such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) acrylate and dimethylaminoethylamide methylacrylate and dimethylaminopropyl methylacrylate; basic heterocyclic monomers such as vinylpyrrolidone, vinylpyridine, and vinylcarbazole; vinyl monomers containing organosilyl groups such as trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, trin-propylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, triethylsilyl (meth) acrylate n-amylsilyl, tri-n-hexylsilyl (meth) acrylate, tri-n-octylsilyl (meth) acrylate, tri-n-dodecyl silyl (meth) acrylate, triphenylsilyl (meth) acrylate, (meth) acrylate tri-pmethylphenylsilyl, tribenzylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate, triisobutylsilyl ^{(meth) acrylate, tri-s-butylsilyl (meth) acrylate, tri-} 2 ^{-methylisopropylsilyl (meth) acrylate, (meth) tri-t-butylsilyl acrylate,} ethyldimethylsilyl (meth) acrylate, n-butyldimethylsilyl (meth) acrylate, diisopropyl-n butylsilyl (meth) acrylate, n-octyldi-n butylsilyl (meth) acrylate, (meth) acrylate diisopropylstearylsilyl, dicyclohexylphenylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate, lauryldiphenylsilyl (meth) acrylate, triisopropylsilyl maleate ethyl, triisopropylsilyl maleate, tri-n-butylsilyl n-butyl maleate, t-butyldiphenylsilyl methyl maleate, t-butyldiphenylsilyl n-butyl maleate, triisopropylsilyl methyl fumarate, tri-isopropylsilyl amyl fumarate, tri-n-butyl fumarate n-butyl, t-butyldiphenylsilyl methyl fumarate and t-butyldiphenylsilyl methyl and t-butyldiphenylsilyl n-butyl fumarate; vinyl monomers containing anhydride groups such as maleic anhydride and itaconic anhydride; vinyl monomers containing carboxyl groups such as acrylic acid, methacrylic acid, crotonic acid, vinyl benzoic acid, fumaric acid, itaconic acid, maleic acid, citraconic acid, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, Monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, monooctyl itaconate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monooctyl fumarate, monoethyl citrate, monohydroxyethyl (meth) acrylate (meth) acrylate, methyl tetrahydroxypropyl (tetrahydroxypropyl) acrylate tetrahydrophthalate, (meth) acrylate monohydroxybutyl tetrahydrophthalate, (meth) acrylate monohydroxyethyl phthalate, (meth) acrylate monohydroxypropyl phthalate, (meth) acrylate monohydroxyethyl succinate, (meth) acrylate (methyl) acrylate monohydroxypropyl monohydroxypropyl succinate, (meth) acrylate (methyl) acrylate monohydroxypropyl monohydroxypropyl maleate (meth) acrylate; unsaturated dicarboxylic acid diester monomers such as dimethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, dibutyl itaconate, and diperfluorocyclohexyl fumarate; cyano group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; vinyl ether monomers such as alkyl vinyl ethers (eg, ^{ethyl vinyl ether, propyl} vinyl ether, butyl vinyl ether, hexyl vinyl ether and 2 ^{-ethylhexyl vinyl ether) and cycloalkyl} vinyl ethers (eg cyclohexyl vinyl ether); vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; aromatic vinyl monomers such as styrene, vinyl toluene, and α-methylstyrene; halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and chlorotrifluoroethylene; polyfunctional monomers such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, di ( meth) acrylate 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate 1,9-nonanediol di (meth) ^{acrylate, 1,} 10 ^{-decanodiol tri (meth) acrylate, trimethylolpropane pentaerythritol tetra (meth) acrylate,} dipentaerythritol hexa (meth) acrylate, allyl methacrylate, triallyl cyanurate, diallyl maleate, and polypropylene glycol diallyl ether. Those listed above can be used alone or in combination thereof

Regarding the viscosity of the resin composition, the monomer (m2) is preferably a monofunctional monomer having an ethylenically unsaturated bond.

From the viewpoint of dissolution rate and resistance to cracking of the coating film, the ^{structural unit (u} 2 ^{) is preferably a unit derived from a (meth) acrylate monomer containing an} oxyethylene group represented by the following formula (2-1). As the (meth) acrylate monomer containing an ^{oxyethylene group, the compounds represented by the following formula (} 2-1 ^{) are preferred.}

Z1- (CH2CH2O) nR21 - (2-1)

(In the above formula, Z1 represents an acryloyloxy or methacryloyloxy group; R21 represents a hydrogen atom or a C1 to C10 alkyl or aryl group; and "n" is an integer from 1 to 15.)

In formula (2-1), when Z1 is an acryloyloxy or methacryloloxy group, the hydrolysis rate tends to be higher if Z1 is an acryloyloxy group, and any acryloyloxy group can be selected based on its dissolution rate.

The C1 to C10 aryl and alkyl groups for R21 are the same as those listed above for R1 and R3 In consideration of water resistance and crack resistance, "n" is preferably an integer from 1 to 10, more preferably from 1 to 5, even more preferably 1 to 3, especially preferably 1 or 2. To achieve a good balance of plasticity, resistance to cracking and peel resistance of the ^{coating film and long-term self-polishing properties, the structural unit (u} 2 ^{) is preferably} a structural unit derived from (meth) acrylate monomers containing hydrophobic groups.

As (meth) acrylate monomers containing hydrophobic groups, alkyl (meth) acrylates are preferred.

The content of the structural unit (u2) is preferably 1 to 80% by mass, more preferably 10 to 70% by mass, even more preferably 20 to 60% by mass relative to the sum (100% by mass) of all structural units.

When the polymer (A) has a structural unit derived from a (meth) acrylate monomer containing an ^{oxyethylene group, the content of said structural unit is preferably} 1 ^{to 80% by mass, more} preferably 5 to 60% by mass , even more preferably 20 to 50% by mass, with respect to the sum of all the structural units. When the content of the structural unit is at the above lower limit or above, the hydrophilic property of the coating film is further improved and the self-polishing properties are further improved. When the content of the structural unit does not exceed the above-mentioned upper limit, the coating film has an appropriate hydrolysis property, long-lasting self-polishing properties are maintained, and antifouling effects are further enhanced.

When polymer (A) includes a structural unit derived from a monomer (m2) other than ^{(meth) acrylate monomer containing an oxyethylene group, the content of said structural unit is preferably} 1 ^to 98% by mass, more preferably from 10 to 98% by mass, even more preferably 10 to 80% by mass, based on the sum of all structural units. When the content of the structural unit is within the above range, the plasticity, the crack resistance and the peel strength of the coating film are improved, and therefore the antifouling effects are further enhanced. When the content of the structural unit does not exceed the mentioned upper limit, the coating film achieves proper hydrolysis property, long-lasting self-polishing properties are maintained, and antifouling effects are further enhanced.

The sum of the structural units (u1) and (u2) is 100% by mass.

The weight average molecular weight (Mw) of the polymer (A) is 2,000 to 100,000, preferably 2,000 to 35,000, more preferably 2,000 to 19,000, even more preferably 3,000 to 16,000. When the weight average molecular weight of the polymer (A) is not more than 19,000, the viscosity of the resin composition is limited to less than 2,000 mPas even if the polymer (A) is contained in an amount of 57% by mass or more. In addition, the antifouling effects of the coating film are excellent. When the weight ^{average molecular weight is} 2,000 ^{or more, the coating film achieves sufficient strength and durability.}

The number average molecular weight (Mn) of the polymer (A) is 1,000 to 30,000, preferably 1,000 to 12,000, more preferably 2,000 to 9,000.

The polydispersity (Mw / Mn) of the polymer (A) is 1.5 to 10.0, preferably 1.5 to 5.0, more preferably 2.2 to 3.0.

The weight average molecular weight and the number average molecular weight of the polymer (A) are determined by gel permeation chromatography (GPC) using polystyrene as a standard resin.

The glass transition temperature (Tg) of the polymer (A) is preferably -20 to 60 ° C, more preferably 0 to 40 ° C. When the Tg of the polymer (A) is less than or equal to the upper limit of the above range, the viscosity of the resin composition is further reduced. When the Tg is at least the lower limit mentioned, the physical properties of the resin coating film are excellent.

The Tg is a value obtained by converting the absolute temperature calculated from the following equation into degrees Celsius (° C).

In the above equation, "wi" represents the mass fraction of monomer (i) of polymer (A) and Tgi represents the glass transition temperature of homopolymer of monomer (i) in polymer (A).

In the above equation, Tg and Tgi are values expressed in absolute temperature (K). Also, Tgi is a value described in "Polymer Handbook, Fourth Edition".

The polymer (A) is preferably a chain polymer that does not have a cross-linked structure. A chain structure reduces the viscosity of a resin composition compared to those with a cross-linked structure.

(Procedure to produce polymer (A))

The following production procedures (a) and (p) can be used to produce a polymer (A).

Production method (a): polymerization of a monomer component containing a monomer (m1). Production process (p): polymerization of a monomeric component including a monomer (m0) having an ethylenically unsaturated bond and a carboxyl group to obtain a polymer (A0) having a group carboxyl and the carboxyl group of the polymer (A0) is converted to a 1- (alkyloxy) ester group, 1- (alkylthio) ester ^{group or 1- (dialkylamino) ester group.}

Production procedure ( a)

The monomer component used in the production process (a) contains at least one monomer (m1) and ^{may further contain one monomer (m} 2 ^).

The monomer content (m1) in the monomer component is preferably 1 to 80% by mass with respect to the sum of all monomers. That is, the polymer (A) is preferably obtained by polymerizing the ^{monomer component containing the monomer (m} 1 ^{) in} 1 ^{to 80% by mass (charged amount) with respect to} the sum of all monomers.

The monomer content (m1) is more preferably 10 to 70% by mass, even more preferably 20 ^{to 60% by mass.}

When the monomer content (m1) is at the above lower limit or above, even better self-polishing properties are achieved for the coating film. When the monomer content (m1) does not exceed the mentioned upper limit, the coating film exhibits appropriate hydrolysis property, long-lasting self-polishing properties are maintained, and antifouling effects are further enhanced.

When the monomer component includes a (meth) acrylate monomer containing an oxyethylene group, it is preferred that its content is 1 to 80% by mass, more preferably 5 to 60% by mass, even more preferably 20 to 50%. by mass with respect to the sum of all monomers. When the content of the monomer is at the above lower limit or above, the coating film exhibits a higher hydrophilic property, and therefore the self-polishing properties are further improved. When the content of the structural unit does not exceed the above-mentioned upper limit, the coating film exhibits appropriate hydrolysis property, long-lasting self-polishing properties are maintained, and antifouling effects are further enhanced.

When the monomer component includes a monomer (m2) other than the (meth) acrylate monomer containing an oxyethylene group, it is preferred that the content of said monomer is 1 to 98% by mass, more preferably 10 to 98% by mass. , even more preferably 10 to 80% by mass with respect to the sum of all the monomers.

The sum of the monomer units (m1) and (m2) (even when there is no monomer (m2)) is 100% by mass. The monomers (m1) and (m2) can be purchased commercially or appropriately synthesized using a known procedure.

A monomer (m1) can be synthesized by converting the carboxyl group of a monomer (m0) to a 1- ^{(alkyloxy) ester,} 1- ^{(alkylthio) ester or} 1- ^{(dialkylamino) ester group.}

Examples of the (m0) monomer are (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, monomethyl maleate, monomethyl fumarate, and the like.

To convert the carboxyl group of a monomer (m0) into a 1- (alkyloxy) ester, 1- (alkylthio) ester or 1- (dialkylamino) ester group, the monomer (m0) can be reacted with a described compound (B) later (addition reactions).

Compound (B) is 1-alkenylalkyl ether, 1-alkenylalkylsulfide or 1-alkenyldialkylamine.

The reaction of a monomer (m0) and a compound (B) proceeds under relatively mild conditions. For example, regardless of the presence of an acid catalyst such as hydrochloric acid, sulfuric acid or phosphoric acid, the desired reactant is obtained by conducting the reaction for 5 to 10 hours while maintaining the reaction temperature between 40 and 100 ° C.

After completion of the reaction, a desired monomer is collected by vacuum distillation under predetermined conditions.

<Compound (B)>

The compound (B) of the present invention is 1-alkenylalkyl ether, 1-alkenylalkylsulfide or 1-alkenyldialkylamine. That is, compound (B) includes an ethylenically unsaturated bond and an ether oxygen atom, a sulfur sulfide atom, or an amine nitrogen atom bonded to one of the carbon atoms of the ethylenically unsaturated bond. As compound (B), those represented by the formula (31), (32) or (33) can be used. These Compounds can be used alone or in combination thereof.

(In the above formulas, "X" represents an ether oxygen atom, a sulfur sulfide atom, or an amine nitrogen atom; R7 represents a hydrogen atom or a C1 to C9 alkyl group; R8 represents an atom of hydrogen or a C10 alkyl group; R9 and R11 represent a C1 to C20 alkyl, cycloalkyl or aryl group, which may or may not be substituted with at least one substituent selected from cycloalkyl, aryl, alkoxy, alkanoyloxy and aralkyl, R10 is a single bond, or a C1 to C9 alkylene group, which may or may not be substituted with at least one substituent selected from cycloalkyl, aryl, alkoxy, alkanoyloxy and aralkyl groups; and R12 is a C1 to C9 alkylene group, which may be or unsubstituted with at least one substituent selected from cycloalkyl, aryl, alkoxy, alkanoyloxy and aralkyl groups).

If a compound represented by the formula (31) is used as the compound (B), the monomer (m1) is obtained as ^{a compound in which R1, R2, R3 and "Z" in the formula (11) correspond, respectively, a CH} 2 ^R 7 ^{, R8, R9 and (H).} In formula (31), the C1 to C9 alkyl group in R7 is the same as the C1 to C10 alkyl group in R1, except that the number of carbon atoms is 9 or less.

R8 and R9 are the same, respectively, as R2 and R3 in formula (11) above.

As for a compound represented by the formula (31), examples of 1 -alkenyl ^{alkyl ethers are vinyl ethers such as alkyl vinyl ethers (for example, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether and} 2- ^{ethyl hexyl vinyl ether) and cycloalkyl vinyl ethers (eg, cyclohexyl vinyl ether);} 1- ^{propenyl ethers such as ethyl-} 1- ^{propenyl ether; and} 1-butenyl ethers such as ethyl-1-butenyl ether. Examples of 1-alkenyl alkyl sulfide are 1 - (ethenylthio) ethane, 1- ^{(ethenylthio) propane,} 1 ^{- (ethenylthio) butane,} 2 ^{- (ethenylthio) butane,} 1 ^{- (ethenylthio)} -2- ^{methylpropane,} 1 ^{- (propylthio ) -} 1 ^-propene, 2- (propylthio) -1-propene and the like. Examples of 1-alkenyl dialkylamine are N, N-dimethylethanamine, N-methyl-N-ethylethanamine, N, N-diethylethanamine, N-vinylpyrrolidine, and the like.

Among those listed above, vinyl ethers and 1-propenyl ethers are preferred.

When a compound represented by the formula (32) is used as the compound (B), the monomer (m1) is obtained as a compound in which R4 and "Z" in the formula (12) correspond, respectively, to CH-R10 and (H).

In formula (32), the C1 to C9 alkylene group in R10 is the same as R4 except that the number of carbon atoms is 9 or less.

Examples of a compound represented by the formula (32) are dihydrofurans such as 2,3-dihydrofuran and 5-methyl-2,3-dihydrofuran; dihydropyrans such as 3,4-dihydro-2H-pyran and 5,6-dihydro-4-methoxy-2H-pyran; dihydrothiophenes such as 2,3-dihydrothiophene; dihydrothiopyrans such as 3,4-dihydro-2H-thiopyran; dihydropyrroles such as 2,3-dihydro-1-methylpyrrole; tetrahydropyridines such as 1,2,3,4-tetrahydro-1-methylpyridine; and the like. If a compound represented by the formula (33) is used as the compound (B), the monomer (m1) is obtained as a compound in which R5, R6 and "Z" in the formula (13) correspond, respectively, to R11 , R12 and (H).

In formula (33), R11 is the same as R5, and the C1 to C9 alkylene group in R12 is the same as R6 except that the number of carbon atoms is 9 or less.

Examples of a compound represented by formula (33) are 1-alkoxy-1-cycloalkylene such as 1-methoxy-1- ^{cyclopentene,} 1 ^-methoxy- 1 ^{-cyclohexene,} 1 ^-methoxy- 1 ^{-ciclohepteno} 1 ^-etoxi- 1 ^{-cyclopentene,} 1 ^-ethoxy- 1- ^cyclohexene, 1 ^-butoxy- 1- ^{cyclopentene and} 1 ^-butoxy- 1- ^cyclohexene; 1 ^-alkoxy- 1- ^{cycloalkylenes containing substituents such as} 1 ^{-ethoxy-3-methyl-1-cyclohexene;} 1 ^{- (alkylthio)} -1- ^{cycloalkylenes such as} 1- ^(methylthio) -1- ^{cyclopentene and} 1- ^(methylthio) -1- ^cyclohexene; 1- (1- ^pyrrolidinyl ) -1- ^{cycloalkylenes such as} 1- (1- ^pyrrolidinyl ) -1- ^{cyclopentene and} 1 ^{- (} 1- ^{pyrrolidinyl)} -1-cyclohexene; and the like.

Compound (B) is a material used to convert a carboxyl group into a 1- (alkyloxy) ester group, a 1- (alkylthio) ester group or a 1- (dialkylamino) ester group. When a carboxylic acid and a compound (B) experience ^{addition reactions, the carboxylic acid is blocked, resulting in a} 1- ^{(alkyloxy) ester,} 1- ^{(alkylthio) ester or} 1- ^{(dialkylamino) ester group.}

Compounds (B) can be purchased commercially or appropriately synthesized.

After polymerization of a monomer as a material for a polymer (A), or after a polymer (A) is formed by polymerizing a monomer as a material for a polymer (A) through a conventional procedure such as suspension polymerization, emulsion polymerization, solution polymerization or the like, the polymer (A) can be obtained as an unreacted compound in which a compound (B) is added in an amount exceeding the equivalent amount for the reaction. The polymer (A) can also be obtained as an unreacted compound in which a compound (B) is added in an amount that exceeds the equivalent amount for a reaction carried out simultaneously with the polymerization by mixing an ethylenically unsaturated monomer containing a carboxyl group (for example, ((meth) acrylic acid), another ethylenically unsaturated monomer, and compound (B). In other words, as long as a compound (B) is finally present in polymer (A), the moment it is Adding a compound (B) is not the problem. However, if a compound (B) is present during a polymerization reaction, since a certain amount of compound (B) undergoes radical polymerization, it is preferred to add a desired amount of compound (B) after completion of polymerization.

[Compound (B) content]

When the content of compound (B) in a resin composition is set to at least 1 mole per 100 mole of the sum of the group 1 - (alkyloxy) ester, group 1 - (alkylthio) ester or 1- (dialkylamino) ester in polymer (A), the storage stability is improved, the crack resistance is excellent, and the dissolution stability is improved. The content is preferably at least 5 moles, more preferably at least 12 moles, even more preferably at least 20 moles, especially preferably at least 40 moles. Furthermore, by keeping the ^{content at} 1000 ^{moles or less, preferably} 800 ^{moles or less, the weatherability and} physical properties of the coating film are kept favorable.

Production procedure (p)

In the production process (p), the monomer component containing the monomer (m0) is first polymerized to obtain a polymer (A0) having a carboxyl group. The monomer component may ^{further contain a monomer (m} 2 ^).

The monomers (m0) and (m2) are the same as those described above.

The preferred content of monomer (m0) in the monomer component is the same as for the monomer (m1) in the monomer component in the production process (a).

The preferred contents of a (meth) acrylate monomer containing an oxyethylene group and another monomer (m2) are the same as described above.

The polymerization of the monomer component can also be carried out in the same way as in the production process (a).

Next, the carboxyl group of the polymer (m0) is converted to a 1- (alkyloxy) ester group, a 1- (alkylthio) ester group or a 1- (dialkylamino) ester group to obtain polymer (A).

To convert the carboxyl group of the polymer (A0) into a 1- (alkyloxy) ester group, 1- (alkylthio) ester group or 1- (dialkylamino) ester group, the polymer (A0) and a compound (B) are subjected to reactions (addition reactions), for example.

Examples of a compound (B) are the same as those listed above.

The reaction of the polymer (A0) and the compound (B) is carried out in the same way as that of the monomer (m0) and the compound (B).

[Procedure to produce polymer (A)]

The polymer (A) of the present invention is produced using the monomers listed above. Any known polymerization process can be employed, such as solution polymerization processes, suspension polymerization, a block polymerization process, and an emulsion polymerization process. In view of the productivity and properties of the coating film, solution polymerization is preferred. Solution polymerization is carried out by a known procedure using a known polymerization initiator.

The polymer (A) is produced by reacting a monomer mixture of the above monomers in the presence of a radical polymerization initiator under a reaction temperature of 60 to 120 ° C for 4 to 14 hours. Examples of radical polymerization initiators are 2,2-azobisisobutyronitrile, 2,2-azobis (2,4- ^{dimethylvaleronitrile),} 2 ^{, 2 -azobis (} 2- ^{methylbutyronitrile), benzoyl peroxide, cumene hydroperoxide,} lauroyl peroxide, di-t-butyl peroxide, t-butyl peroxy-2-ethylhexanoate, and the like. If appropriate, a known chain transfer agent can be added. Examples of a chain transfer agent are mercaptans such as n-dodecyl mercaptan, thioglycolic acid esters such as octyl thioglycolate, amethylstyrene dimer, terpinolene, and the like. In addition, generic organic solvents such as toluene, xylene, methyl isobutyl ketone, and n-butyl acetate can be used.

The content of polymer (A) in the resin composition of the present invention is preferably at least 57% by mass, more preferably at least 59% by mass, even more preferably at least 61% by mass, relative to the total content of the resin composition. When the content of polymer (A) is at least the lower limit of said range, the relative amount of solvent is lower, thus reducing the VOC content in the antifouling coating composition when an antifouling agent is incorporated into the resin composition.

The upper limit of the polymer (A) is determined according to the weight average molecular weight of the polymer (A), its glass transition temperature, the presence of a crosslinked structure or the like, and it is preferred that it is 85% by mass or less, more preferably 75% by mass or less to adjust the viscosity of the resin composition to less than 2,000 mPas.

<Solvent>

The solvent is not specifically limited as long as it can dissolve the polymer (A). Examples are hydrocarbon-based solvents such as toluene and xylene; ketone-based solvents such as methyl isobutyl ketone; ester-based solvents such as n-butyl acetate, propylene glycol monomethyl ether acetate, and ethyl 3-ethoxypropionate; and the like. They can be used alone or in combination thereof. The lower limit of a solvent is determined according to the weight average molecular weight of the polymer (A), its glass transition temperature, the presence of a crosslinked structure or the like, and preferably is at least 15% by mass, plus preferably at least 25% by mass, so that the viscosity of the resin composition is less than 2,000 mPas.

<Other components>

The resin composition of the present invention may further include components other than a polymer (A). Examples of other components are the same as the antifouling coating composition described below.

It is preferred that the content of other components is 200% by mass or less of polymer (A), and the content may even be zero% by mass.

In addition, to improve storage stability, it contains at least one type of additive selected from compounds that react with acids, acidic compounds and basic compounds.

When the storage stability of a resin containing a 1- (alkyloxy) ester group, a 1- (alkylthio) ester group or a 1- (dialkylamino) ester group is reduced, the probable reasons are an increase in Tg caused by a carboxylic acid produced by unwanted decomposition of said group in the resin or coating composition, and an increase in the viscosity of the resin or coating composition caused by crosslinking of said group with the component of the coating composition. Furthermore, solution stability and water resistance can be reduced when free carboxylic acids are produced. Furthermore, the carboxylic acid produced acts as an acid catalyst to advance hydrolysis reactions and thereby accelerates decomposition. Therefore, when a compound that can react with acid is added, the compound traps the carboxylic acid produced, thus improving storage stability. Examples of compounds that can react with acid are basic compounds, compounds containing epoxy groups, a compound (B), and the like.

Examples of a basic compound are dimethylamine, diethylamine, trimethylamine, triethylamine, aniline, pyridine, and the like. Examples of a compound containing an epoxy group are 2-ethyloxyran, 2,3-dimethyloxyran, 2,2-dimethyloxyran, glycidyl (meth) acrylate, glycidyl α-ethylacrylate, 3,4-epoxybutyl (meth) acrylate and Similar. As compound (B), those described above in formula (31), (32) or (33) can be used. It is preferred that the content of compound (B) in the resin composition is in the range described above.

As the compound that can react with an acid, a compound (B), more preferably 1-alkenylalkyl ether, is preferable from the viewpoint of storage stability. By incorporating 1-alkenylalkyl ether, excellent crack resistance and solution stability are achieved.

Furthermore, since in the high pH or low pH region the decomposition of a 1- (alkyloxy) ester group, a 1- (alkylthio) ester group or a 1- (dialkylamino) ester group is accelerated, and in the region of High pH reduces the reactivity of compound (B) and a carboxylic acid, the storage stability decreases. To improve the storage stability, it is preferred to add a basic compound or an acidic compound in such an amount to fix the pH ^{in the water to be 2 to 12, more preferably} 6 ^{to 9. Thus, it can be adjusted the pH to the} resin composition and the coating composition.

Preferred examples of a basic compound are those listed above. Examples of an acid compound are abietic acid, neoabietic acid, palustric acid, pmaric acid, isopimaric acid, levopimaric acid, dextropimaric acid, sandaracopimaric acid, acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, linoleic acid, oleic acid. , chloroacetic acid, fluoroacetic acid and the like.

<Decomposition rate of the structure represented by formula (1), (2) or (3) in the polymer (A) after storage at 40 ° C for 30 days>

When the structure represented by formula (1), (2) or (3) in the polymer (A) is established to have a decomposition rate of 20% or less after storage of the composition at 40 ° C for 30 days , storage stability and dissolution stability are provided for the resin composition or antifouling coating composition.

It is preferred that the decomposition rate is 7% or less, more preferably 4% or less, even more preferably 3% or less, especially preferably 2% or less.

The decomposition rate of the structure represented by formula (1), (2) or (3) is defined as shown in the following equation: the theoretical solid acid number (b), obtained assuming that no structure decomposes in (1), (2) or (3), it is subtracted from the measured solid acid number (a), and the resulting value is divided by the theoretical solid acid number (c), obtained assuming that the entire structure is decomposed of formula (1), (2) or (3) contained in a sample.

(decomposition rate) = {(measured solid acid number (a)) - (index

^{theoretical solid acid (b))} / (theoretical solid acid number (c)) *} 100

The measured solid acid numbers will be described later under the heading of acid number measurement. Theoretical solid acid numbers are obtained by the following equation.

(theoretical solid acid number) = 1 (561 * 100 / Mwi * wi)

In the above equation, "wi" represents the mass fraction of the monomer containing an acid functional group (i) of a copolymer (A), and "Mwi" indicates the molecular weight of the monomer containing an acid functional group.

When the structure is decomposed, the acid number is calculated as a monomer that has an acid functional group.

When the structure is not decomposed, the acid number is calculated as a monomer without any acid functional groups.

<Viscosity>

The viscosity of a resin composition of the present invention is preferably less than 2000 mPas, more preferably 1000 mPas, even more preferably 600 mPas, when determined at 25 ° C using a Brookfield viscometer. When the viscosity of a resin composition does not exceed the mentioned upper limit, since an antifouling agent is incorporated without adding a dilution solvent to the resin composition, a low VOC antifouling coating composition is obtained.

The lower limit of the viscosity of the resin composition is not specifically limited, but 100 mPa s or more is preferred when considering the physical properties of the coating film.

The viscosity of a resin composition can be adjusted by controlling its amount of solids (content of polymer (A) and other components), the weight average molecular weight of the polymer (A), the glass transition temperature, the presence of a structure cross-linked or the like. For example, when the amount of solids, especially the content of polymer (A), is lower, the resin composition tends to have a lower viscosity. Furthermore, it is more likely that a lower weight average molecular weight of the polymer (A), or a lower glass transition temperature, produce a lower viscosity.

The resin composition of the present invention is prepared using a known procedure; for example, a polymer (A) is synthesized using the above-mentioned production method (a) or (p), and the obtained polymer (A) is mixed with a solvent and other components as required.

At that time, it is preferable to add other components so that the content of polymer (A) in the resin composition is at least 57% by mass (more preferably at least 59% by mass), and that the viscosity of the resin composition resin is less than 2,000 mPas (more preferably less than 1,000 mPas). When the viscosity is less than 2,000 mPas, an antifouling agent or the like is well incorporated into the resin composition without adding more solvent to form an antifouling coating composition. As a result, the antifouling coating composition has a lower VOC content (eg 410 g / l or less).

The resin composition of the present invention is used to form an antifouling coating composition and also for an antifog coating composition or the like.

[Antifouling coating composition]

The antifouling coating composition of the present invention contains the above-mentioned resin composition of the present invention and an antifouling agent.

The antifouling coating composition may also contain other components in addition to a polymer (A) and an antifouling agent. The other components may be those derived from the resin composition of the present invention or they may be others (such as those incorporated during the production of an antifouling coating composition).

The antifouling coating composition of the present invention may contain a solvent that is not derived from the resin composition.

<Antifouling agent>

As for antifouling agents, those available are inorganic, organic or the like, and one or two or more types are appropriately selected for use according to the desired properties.

Examples are copper-based antifouling agents such as cuprous oxide, copper thiocyanate, and copper powder; compounds of other metals (lead, zinc, nickel, etc.); amine derivatives such as diphenylamine; other compounds such as nitrile compounds, benzothiazole compounds, maleimide compounds, and pyridine compounds; and the like. They can be used alone or in combination thereof.

More specific examples of antifouling agents are 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, manganese ethylene bis dithiocarbamate, zinc dimethyldithiocarbamate carbamate, 2-methylthio-4- t- ^butylamino- 6- ^{cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyl dichlorophenylurea,} zinc ethylene bis-dithiocarbamate, copper rhodanide, 4,5-dichloro-2-n -octyl-3 (2H) -isothiazolone, N- (fluorodichloromethylthio thio) phthalimide, N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio thio) sulfamide, 2-pyridinothiol-1-oxide zinc salt, Tetramethylthiuram disulfide, Cu-10% Ni solid solution alloy, 2,4,6-trichlorophenyl maleimide, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 3-iodo-2-propynyl butylcarbamate , diiodomethyl-p-tolyl sulfone, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, phenyl (bispyridyl) bismuth dichloride, 2- (4-thiazolyl) -benzimidazole, medetomidine, pyridine-triphenylborane and the like.

Among those listed above, it is preferred to include at least one type selected from cuprous oxide, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (hereinafter also referred to as "agent ^{antifouling (} 1 ^{) ") and medetomidine.}

When cuprous oxide and antifouling agent (1) are used together, the composition ratio (mass ratio) is preferably cuprous oxide / antifouling agent (1) = 80/20 to 99/1, more preferably 90/10 to 99 /1. Another antifouling agent can also be combined with one or both of the cuprous oxide and the ^antifouling agent (1 ^).

The amount of antifouling agent in an antifouling coating composition is not specifically limited, but is preferably 10 to 200 parts by mass, more preferably 50 to 150 parts by mass, per 100 parts by mass of polymer (A). When the content of the antifouling agent is at least the mentioned lower limit, the coating film further exhibits excellent antifouling effects, and when the content does not exceed the mentioned upper limit, the physical properties of the coating film are excellent.

<Other components>

Other components of the antifouling coating composition can be a resin other than polymer (A), for example.

The other resin does not contain a functional group (I), and is a thermoplastic resin, for example.

Preferably, the antifouling coating composition of the present invention contains a thermoplastic resin. When prepared with a thermoplastic resin, the physical properties of the coating film are improved, such as resistance to cracking and resistance to water.

Examples of a thermoplastic resin are chlorinated paraffins; chlorinated polyolefins such as chlorinated rubber, chlorinated polyethylene, and chlorinated polypropylene; polyvinyl ether; polypropylene sebacate; partially hydrogenated terphenyl; and polyvinyl acetate; alkyl poly (meth) acrylates such as methyl (meth) acrylate copolymers, ethyl (meth) acrylate copolymers, propyl (meth) acrylate copolymers, butyl (meth) acrylate copolymers and (meth) copolymers cyclohexyl acrylate; polyether polyol; alkyd resins; polyester resins; vinyl chloride resins such as vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinylpropionate copolymers vinyl chloride-isobutyl vinyl ether copolymers vinyl chloride-isopropyl vinyl ether copolymers and vinyl chloride-ethyl copolymers vinyl ether; silicone oil; waxes; solid fats at room temperature other than waxes; room temperature liquid fats and oils, such as castor oil and its purified products; petroleum jelly; liquid paraffin; rosin, hydrogenated rosin; naphthenic acid, fatty acids and their divalent metal salts; and the like. Examples of waxes are waxes of animal origin such as beeswax; waxes of vegetable origin; semi-synthetic waxes such as amide waxes; synthetic waxes such as polyethylene waxes and oxidized polyethylene waxes. These thermoplastic resins can be used alone or in combination thereof.

Among those listed above, chlorinated paraffin is preferred as it acts as a plasticizer and contributes to improving the crack resistance and peel resistance of the coating film.

As anti-settling agents and anti-sagging agents that contribute to improving the storage stability and pigment dispersibility of antifouling coating compositions, it is preferred to use organic waxes such as semi-synthetic waxes and synthetic waxes, more preferably a polyethylene wax, oxidized polyethylene wax or polyamide wax.

The amount of thermoplastic resin in an antifouling coating composition is not specifically limited, but is preferably 0.1 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of polymer (A ). When the content of a thermoplastic resin is at least the mentioned lower limit, the physical properties such as crack resistance and water resistance of the coating film are improved, and when the content does not exceed the mentioned upper limit, the property hydrolysis is even better.

The antifouling coating composition of the present invention may include silicon compounds such as dimethylpolysiloxane and silicone oil, or fluorine-containing compounds such as fluorinated hydrocarbons and the like in order to impart lubricity to the surface of the coating film and prevent seizure. adhesion of organisms. Examples of silicone oil are "KF96" (Shin-Etsu Chemical Co., Ltd.), "SH200" (Dow Corning Toray Co., Ltd.), "TSF451" (Toshiba Silicones Co., Ltd.), "D ^c 200 "(Dow Corning Corporation)," Fluid 47 "(Rhone-Poulenc SA, France)," KF50, Kf54 "(Shin-Etsu Chemical)," SH510, s H550, SH710 "(Dow Corning Toray) and the like.

The antifouling coating composition of the present invention may further include various types of pigments, dehydrating agents, defoaming agents, leveling agents, pigment dispersing agents (eg, anti-settling agents), anti-sagging agents, mattifying agents, ultraviolet absorbers, antioxidants, heat enhancers, slip agents, preservatives, plasticizers, viscosity control agents, and the like.

As for the pigment, zinc oxide, talc, silica, barium sulfate, potassium feldspar, aluminum hydroxide, magnesium carbonate, mica, carbon black, red iron oxide, titanium oxide, phthalocyanine blue, kaolin can be used. , plaster and the like. In particular, zinc oxide and talc are preferred.

As the dehydrating agent, silicate-based, isocyanate-based and orthoester-based dehydrating agents, inorganic dehydrating agents and the like can be used. More specifically, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, orthoboric ester, tetraethyl orthoformate, anhydrous gypsum, calcined gypsum, synthetic zeolite (molecular sieve) and the like can be used. Moisture is trapped by incorporating a dehydrating agent into the antifouling coating composition, thereby improving its storage stability.

As for an anti-settling and anti-sagging agent, instead of using thermoplastic resins, bentonite, fine silica, stearate salt, lecithin salt, alkylsulfonic acid salts and the like can be used. Examples of plasticizers other than thermoplastic resins are phthalic acid ester plasticizers such as dioctyl phthalate, dimethyl phthalate, dicyclohexyl phthalate, and diisodecyl phthalate; aliphatic dibasic acid ester plasticizers such as isobutyl adipate and dibutyl sebacate; glycol ester plasticizers such as diethylene glycol dibenzoate and pentaerythritol alkyl esters; phosphoric acid ester plasticizers such as tricresyl phosphate (TCP), triaryl phosphate, and trichloroethyl phosphate; epoxy plasticizers such as epoxy soybean oil and epoxy octyl stearate; organic tin-based plasticizers such as dioctyltin laurate and dibutyltin laurate; trioctyl trimellitate, triacetylene, and the like. By incorporating a plasticizer into the antifouling coating composition, the crack resistance and peel resistance of the coating film are improved. Among the above plasticizers, t Cp is preferred.

<Change in viscosity of coating composition after 90 days>

From the viewpoint of storage stability, it is preferred that the change in viscosity of a ^{coating composition is} 2,000 ^{% or less, more preferably} 1,000 ^{% or less, even more} preferably 400% or less, preferably especially 200% or less, as determined using a Brookfield viscometer after storage at 40 ° C for 90 days.

<VOC content>

The VOC content of the antifouling coating composition of the present invention is preferably 410 g / l or less, more preferably 400 g / l or less, even more preferably 380 g / l or less. The VOC content is obtained from the following equation using the specific gravity values of an antifouling coating composition and the non-volatile content.

VOC content (g / l) = composition specific gravity x1000x (100-non-volatile content) / 100 The specific gravity and non-volatile content of an antifouling coating composition are determined by the procedures described below in the examples.

The VOC content can be adjusted by changing the amount of solvent.

<Viscosity>

The viscosity of the antifouling coating composition of the present invention is preferably less than 3,000 mPas, more preferably less than 2,000 mPas, even more preferably less than 1,500 mPas. When the viscosity of the antifouling coating composition does not exceed the mentioned upper limit, it is easier to apply the coating composition.

The lower limit is not specifically limited, but is preferably 100 mPa s or more considering the physical properties of the coating film.

The viscosity of an antifouling coating composition is adjusted by modifying the viscosity of the resin composition, the amount of solvent in the resin composition, and the like.

The antifouling coating composition of the present invention is prepared by adding an antifouling agent and other components and solvents as desired to the resin composition of the present invention.

The antifouling coating composition of the present invention is used to form a coating film (antifouling coating film) on surfaces of a substrate such as ships, various fishing nets, port facilities, oil fences, bridges, and underwater structures such as underwater bases.

The coating film using the antifouling coating composition of the present invention can be applied directly to the surface of the substrate or to the base coating film formed on the substrate.

Examples of basecoat films are wash primers, rubber chloride-based and epoxy-based primers, intercoats, and the like.

Any known method can be used to form the coating film. For example, the antifouling coating composition is applied to the surface of the substrate or to the base coat of the substrate using a brush, spray or roller, or by dipping the substrate into the composition. Then it dries the coating film.

The amount of antifouling coating composition to be applied is generally set to make a coating film 10 to 400 µm thick when dry.

The coating film dries at room temperature, but heat can be applied if necessary.

EXAMPLES

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples. The parts in the examples refer to parts by mass. Furthermore, the content of a structural unit derived from a monomer having the structure represented by formula (1), (2) or (3) contained in a polymer (A) was determined from the charged amount of a monomer as material, assuming all monomer is polymerized. The examples were evaluated based on the procedures shown below.

[Measurement of acid value]

Approximately 4.0 grams of a sample (A (g)) were weighed into a beaker, to which 50 ml of a solution containing toluene and 95% ethanol in a 50/50 ratio was added. The mixture was put in an airtight container and stirred for 5 minutes. A Hiranuma automatic titrator (AutoTitrator COM-1600) was used to perform a potentiometric titration with a 0.5 mol / L potassium hydroxide solution (ethanol solution), manufactured by Kishida Chemical Co., Ltd., with a factor (f) 1.003 at 20 ° C. The end point was established at the point of maximum slope of the titration curve (titration volume = B (ml), KOH solution titer = f). Meanwhile, the same procedure was carried out with a blank sample (titration volume = C (ml)), and the acid number was calculated by the following equation.

Solid acid number (mgKOH / g) = {(B-C) x 0.5 x 56.11 xf} / A / solid component.

[Brookfield viscosity]

A sample was loaded into a 150 ml glass bottle and it was immersed for at least 2 hours in a thermal bath with a controlled temperature of 25.0 ± 0.1 ° C to keep the sample at a constant temperature. Viscosity was measured using the TVB-10 viscometer, manufactured by Toki Sangyo Co., Ltd., at a rotation speed of 60 rpm using a selected rotor.

[Non-volatile content (solid component)]

In an aluminum dish, 0.50 grams of a sample (resin composition or antifouling coating composition) was weighed and 3 ml of toluene was added using a dropper to spread the composition evenly over the bottom of the dish in order to dry. preliminary sample. Preliminary drying was carried out to spread the sample evenly on the plate so that the sample evaporated more easily during the final drying. During preliminary drying, the sample and toluene were heated and dissolved on the plate in a 70-80 ° C water bath to dry the sample by evaporation. Then, final drying of the sample was carried out for 2 hours using a hot air blower at 105 ° C. The non-volatile content (solid component) was calculated from the mass of the sample before preliminary drying (mass before drying) and the mass after final drying (mass after drying) using the following equation.

^{non-volatile content (% by mass) = mass after removal / mass before drying x} 100 [Gardner viscosity]

A sample was filled to the indicator line of a dry viscometer tube, which was then stoppered with a cork. The ^{tube with the sample was vertically immersed for at least} 2 ^{hours in a temperature-} controlled thermal bath (25.0 ± 0.1 ° C) to keep the sample at a constant temperature. A reference tube and the sample tube were simultaneously rotated 180 degrees, and the increasing velocities of the bubbles in both tubes were compared to determine the viscosity.

[Weight average molecular weight (Mw), number average molecular weight (Mn)]

Mw and Mn were determined by gel permeation chromatography (GPC) (HLC-8220, manufactured by Tosoh Corporation) using dimethylformamide (DMF) with 20 mM LiBr as eluent. ^{TSKgel aM (7.8 mm x} 30 ^{cm, manufactured by Tosoh) and TSK protection column (6.0 mm x} 4 ^{cm, manufactured by} Tosoh) were also used. To prepare the calibration curves, F288 / F1 / F28 / F80 / F40 / F2 / A1000 (standard polystyrenes, manufactured by Tosoh) and styrene monomers were used.

[Specific gravity]

An antifouling coating composition was filled into a 100 ml specific gravity bottle to determine its mass at 25 ° C so that its specific gravity was calculated.

[Storage stability test]

A resin composition or antifouling coating composition was filled into a 150 ml glass bottle to determine its viscosity by the aforementioned Brookfield viscometer directly after each composition was prepared and after each composition was stored for 30 days and 90 days in a thermal bath adjusted to have a temperature of 40 ° C. Then, the rate of viscosity change was calculated for each resin composition and coating composition.

[VOC content]

Using the values of specific gravity and non-volatile content of an antifouling composition, the VOC content of the antifouling coating composition was calculated using the following equation.

VOC content (g / l) = specific gravity of the composition x1000x (100-non-volatile content) / 100 [Static antifouling performance]

A sample plate was prepared by brush coating an antifouling coating composition to have a dry film thickness of 120 pm on a 150mm x 70mm x 1.6mm (thickness) sandblasted steel plate. , on which an anticorrosive coating was previously applied. The ^{sample plate was immersed in seawater and kept there for} 6 ^{months. Then, the relationship between} the area in which the marine organisms adhered (adhesion area of marine organisms) and the total area of the coating film was obtained, and the static antifouling performance of the coating film on the basis of the following criteria.

A: The adhesion area of marine organisms is 10% or less.

B: the adhesion area of marine organisms is greater than 10% but equal to or less than 20%.

C: the adhesion area of marine organisms is greater than 20% but equal to or less than 40%.

D: the adhesion area of marine organisms is greater than 40%.

[Coating film consumption rate test]

A sample plate was prepared by coating an antifouling composition with an applicator to have a 120 µm dry film thickness on a 50 mm x 50 mm x 2 mm (thickness) hard vinyl chloride plate. When the sample plate was dried, it was installed on a rotating drum to be immersed in seawater. The sample plate on the drum was rotated at a peripheral speed of 7.7 m / s (15 knots). The film thickness was ^{measured after 3 months and} 6 ^{months and, from each measured thickness, the consumed film thickness} (120 ^{pm minus the measured thickness (pm)) was calculated.}

[Water resistance test]

A sample plate was prepared by coating an antifouling composition to have a dry film thickness of 120 µm on a glass substrate. The sample plate was immersed in filtered sterile seawater for one month and dried for one week at a room temperature of 20 ° C. The surface of the coating film was observed and evaluated based on the following criteria.

A: Absolutely no cracking or peeling is observed.

B: cracking is observed in some portions.

C: cracking and detachment are observed in some portions.

D: cracking and spalling are observed over the entire surface.

Production example M1: (m1)]

A mixture was prepared with 150.2 parts (1.5 mol) of butyl vinyl ether, 0.24 parts of hydroquinone and 0.47 parts of phenothiazine and stirred homogeneously at room temperature. Low air flow (10 ml / min), was added ^dropwise drop 86.1 ^{parts (1.0 mol) of methacrylic acid while the temperature of the reaction mixture was maintained at} 60 ° C or less. After the dropping was complete, the temperature of the reaction mixture was raised to 80 ° C and the mixture was reacted for 5 hours. Next, 264.5 parts (3.0 mol) of t-butyl methyl ether were mixed into the reaction mixture and the organic phase was extracted once with 350 parts of a 20 mass% potassium carbonate solution. Then, 0.06 part of 4-benzyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl was added. to the organic phase and the low volatile content was distilled off using an evaporator. After distilling off the residue in vacuo, 166.9 parts (0.91 mol) of 1 -butoxyethyl methacrylate (ml) with a boiling point of 70 ° C / 5 torr were obtained.

[Production example M2: (m2)]

A mixture of 90.1 parts (0.9 mol) of isobutyl vinyl ether, 0.14 part of hydroquinone and 0.28 part of phenothiazine was prepared and stirred homogeneously at room temperature. Under air flow (10 ml / min), 51.7 parts (0.6 mol) of methacrylic acid was added dropwise while the temperature of the reaction mixture was kept at 60 ° C or less. After the dropping was complete, the temperature of the reaction mixture was raised to 80 ° C and the ^{mixture was reacted for} 6 ^{hours. Then, 158.7 parts (1.8 mol) of t-butyl methyl ether were mixed into the reaction mixture and the organic phase was extracted once with} 200 ^{parts of a} 20 mass% potassium carbonate solution. Then, 0.03 part of 4-benzyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl was added to the organic phase and the low volatile content was distilled off using an evaporator. After vacuum distillation of the residue, 97.5 parts (0.52 mol) of 1-isobutoxyethyl methacrylate (m2) with a boiling point of 60 ° C / 3 torr were obtained.

[M3 production example: (m3)]

A mixture of 138.8 parts (1.1 mol) of cyclohexyl vinyl ether, 0.28 part of hydroquinone and 0.53 part of phenothiazine was prepared and stirred homogeneously at room temperature. Low air flow (10 ml / min), was added ^dropwise drop 86.1 ^{parts (1.0 mol) of methacrylic acid while the temperature of the reaction mixture was maintained at} 60 ° C or less. After the dropping was complete, the temperature of the reaction mixture was raised to 80 ° C and the mixture was reacted for 5 hours. Next, 220.4 parts (2.5 moles) of t-butyl methyl ether were mixed into the reaction mixture and the organic phase was extracted once with 135 parts of a 20 mass% potassium carbonate solution. Then, 0.06 part of 4-benzyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl was added to the organic phase and the low volatile content was distilled off using an evaporator. After vacuum distillation of the residue, 160.0 parts (0.75 mol) of 1- (cyclohexyloxy) ethyl methacrylate (m3) with a boiling point of 92 ° C / 5 torr were obtained.

[M4 production example: (m4)]

A mixture of 171.9 parts (1.1 mol) of 2-ethylhexyl vinyl ether, 0.32 part of hydroquinone and 0.61 part of phenothiazine was prepared and stirred homogeneously at room temperature. Low air flow (10 ml / min), was added ^dropwise drop 86.1 ^{parts (1.0 mol) of methacrylic acid while the temperature of the reaction mixture was maintained at} 60 ° C or less. After the dropping was complete, the temperature of the reaction mixture was raised to 80 ° C and the mixture was reacted for 5 hours. Subsequently, 264.5 parts (3.0 moles) of t-butyl methyl ether were mixed into the reaction mixture and the organic phase was extracted once with 135 parts of a 20 mass% potassium carbonate solution. Then, 0.07 part of 4-benzyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl was added to the organic phase and the low volatile content was distilled off using an evaporator. After vacuum distillation of the residue, 207.0 parts (0.85 mol) of 1- (2-ethylhexyloxy) ethyl methacrylate (m4) with a boiling point of 99 ° C / 3 torr were obtained.

[M5 production example: (m5)]

A mixture of 75.7 parts (0.9 mol) of 3,4-dihydro-2H-pyran, 0.13 part of hydroquinone and 0.26 part of phenothiazine was prepared and stirred homogeneously at room temperature. Under air flow (10 ml / min), 51.7 parts (0.6 mol) of methacrylic acid (MAA) was added dropwise while the temperature of the reaction mixture was kept at 60 ° C or less. After the dropping was complete, the temperature of the reaction mixture was raised to 80 ° C and the mixture was reacted for 12 hours. Then, 158.7 ^{parts (} 1.8 ^{mol) of t-butyl methyl ether were mixed into the reaction mixture and the organic phase was extracted once with} 200 ^{parts of} a 20 mass% potassium carbonate solution. Then, 0.03 part of 4-benzyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl was added to the organic phase and the low volatile content was distilled off using an evaporator. After distilling off the residue in vacuo, 75.7 parts (0.44 mol) of 2-tetrahydropyranyl methacrylate (m5) with a boiling point of 76 ° C / 3 torr were obtained.

^{[Production example M} 6 ^{: (m} 6 ^)]

A mixture was prepared with 64.9 parts (0.9 moles) of ethyl vinyl ether, 0.12 parts of hydroquinone and 0.24 parts of phenothiazine and stirred homogeneously at room temperature. Under air flow (10 ml / min), 51.7 parts (0.6 mol) of methacrylic acid was added dropwise while the temperature of the reaction mixture was kept at 30 ° C or less. After the dripping was complete, the mixture was kept at room temperature and reacted for 4 hours. Then, 158.7 parts (1.8 mol) of t-butyl methyl ether were mixed into the ^{reaction mixture and the organic phase was extracted once with 160 parts of a} 20 mass ^{% potassium carbonate solution.} Then, 0.05 part of 4-benzyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl was added to the organic phase and the low volatile content was distilled off using an evaporator. After distilling off the residue in vacuo, ^{68.2 parts (0.43 mol) of 1-ethoxyethyl methacrylate (m} 6 ^{) with a boiling point of 43 ° C / 3 torr were obtained.}

[Production example B-1]

In a reaction vessel equipped with stirrer, temperature regulator and dripping system, 75 parts of xylene were charged and the temperature was raised to 85 ° C while stirring the contents. Next, 10.0 parts of methyl acrylate, 40.0 parts of methoxyethyl methacrylate, 50.0 parts of 1-butoxyethyl methacrylate prepared in Production Example M1 and 1.3 parts of AIBN were mixed, and the mixture were added dropwise over 4 hours at a constant rate. After completion of the dripping, 0.5 part of peroxy-t-butyl octoate and 2 parts of xylene were added dropwise four times at 30 minute intervals and further stirred for one hour. Then 7.3 parts of butyl vinyl ether, 6.7 parts of xylene and 3 parts of butyl acetate were added. Accordingly, the resin composition (B-1) containing (co) polymer (A-1) was obtained with a solids content of 50.2% and a Gardner viscosity of G. With respect to the composition of the resin (B-1), its decomposition rate at 40 ° C after 30 days, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are shown in Tables 1 and 2.

^{Examples B} -8 ^{and B-9 and the corresponding antifouling compositions are in accordance with the invention.} All other examples are reference or comparative examples.

[Production examples B-2 to B-16, B-18, B-19]

The resin compositions (B-2 to B-16, B-18 and B-19) were prepared the same as the resin composition (B-1) except for the loaded amounts specified, respectively, in Tables 1 and 2. For each of the ^{resin compositions obtained (B} -2 ^{to B-16, B-18 and B-19), the solid component (% by mass), the} Gardner viscosity, the decomposition rate after storage at 40 ° C for 30 days, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are shown in Tables 1 and 2.

[Production example B-17]

In a reaction vessel equipped with stirrer, temperature regulator and dripping system, 44.4 parts of propylene glycol acetate monomethyl ether were charged and the temperature was raised to 85 ° C while stirring the contents. Next, 17.5 parts of methyl acrylate, 20.0 parts of ethyl acrylate, 37.5 parts of 2-methoxyethyl methacrylate, 11.6 parts of methacrylic acid and 1.5 parts of AIBN were mixed, and the mixture was dropped over 4 hours at a constant rate. After completion of the dripping, 0.5 part of peroxy-t-butyl octoate and 0.5 part of propylene glycol acetate monomethyl ether were added four times at 30 minute intervals and stirred for another hour. Then 67 parts of butyl vinyl ether was added and the mixture was stirred for 10 hours. Accordingly, a resin composition (B-17) containing (co) polymer (A-17) with a solids content of 50.5% and a Gardner viscosity of FG was obtained. Regarding the composition of the resin (B-17), its decomposition rate after storage at 40 ° C for 30 days, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are shown in Tables 1 and 2.

The proportions (mole%) in the tables indicate the following. (total molar number of monomer in formula (31), (32), (33)) / (total molar number of structural units having the structure represented by formula (1), (2), (3))

The abbreviations in Tables 1 and 2 refer to those listed below.

MMA: methyl methacrylate

EA: ethyl acrylate

2-MTA: 2-methoxyethyl acrylate

2-MTMA: 2-methoxyethyl methacrylate

MAA: methacrylic acid

AIBN: 2,2'-azoisobutyronitrile

AMBN: 2,2'-azobis-2-methylbutyronitrile

[Examples 1 to 19, Comparative Examples 1 to 2]

Resin compositions B-1 to B-19, antifouling agents and the like were mixed to have the proportions specified in Tables 3 and 4 using a high speed disperser. Accordingly, antifouling coating compositions were respectively obtained.

The results of the evaluation of the antifouling coating compositions are shown in Tables 3 and 4.

In Tables 3 and 4, the numerical values indicating composition ratios in the composition column each refer to the amount (parts) incorporated into the composition. The amount of a polymer solution in Tables 3 and 4 is the total amount of the solution.

The abbreviations used in Tables 3 and 4 refer to those listed below.

Antifouling agent (1): 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1 H-pyrrole-3-carbonitrile

Additive (1): Toyoparax 150 (chlorinated paraffin, manufactured by Tosoh)

Additive (2): Disparlon 4200-20 (polyethylene oxide wax, manufactured by Kusumoto Chemicals, Ltd.)

Additive (3): Disparlon A603-20X (polyamide wax, manufactured by Kusumoto Chemicals).

Examples 1 to 17 showed excellent long-lasting antifouling effects, while exhibiting excellent solution stability, crack resistance, and storage stability.

When a composition (Comparative Example 1) did not include any monomer-derived structural units having the structure represented by formula (1), (2) or (3), the results of the consumption rate and static antifouling performance tests of the coating film were low and the long-term self-polishing properties in the wear rate tests of the coating film were insufficient. When the decomposition rate of a composition (Comparative Example 2) was more than 20% after storage at 40 ° C for 30 days, its crack resistance, dissolution stability or storage stability were considered insufficient.

INDUSTRIAL APPLICABILITY

In accordance with the present invention, there is provided a resin composition for producing a low VOC antifouling coating composition having excellent storage stability and coating ability, such that said antifouling coating composition is provided to form a film of coating that exhibits high dissolution stability and self-polishing properties, while preventing excessive film consumption and flaws to achieve long-lasting antifouling effects. Therefore, the antifouling coating composition of the present invention is suitable for application to marine structures, and its industrial applications are quite significant.

Claims (13)

1. Resin composition, configured to understand a polymer (A), and at least one component selected from acidic compounds, basic compounds and compounds that can react with an acid, wherein the polymer (A) comprises at least one structural unit derived from a monomer having the structure represented by the following formula (1), (2) or (3), and wherein, after storage of the resin composition at 40 ° C for 30 days, the decomposition rate of the structure represented by formula (1), (2) or (3) in the polymer (A) is 20% or less, the decomposition rate of the structure represented by formula (1), (2) or (3) is defined as: (decomposition rate) = {(measured solid acid number (a)) - (solid acid number theoretical (b))} / (theoretical solid acid number (c)) * 100 (theoretical solid acid number) = 1 (561 * 100 / Mwi * wi) wherein, "wi" represents the mass fraction of the monomer containing an acid functional group (i) of a copolymer (A), and "Mwi" indicates the molecular weight of the monomer containing an acid functional group, the monomer containing an acid functional group (i) is produced when the structure represented by the formula (1), (2) or (3) decomposes, and the measured solid acid number (a) is carried out according to the following procedure: in a beaker, about 4.0 grams of a sample (A (g)) are weighed, in which 50 ml of a solution containing toluene and 95% ethanol in a 50/50 ratio are added, the mixture is placed in an airtight container and stirred for 5 minutes, An automatic Hiranuma titrator (AutoTitrator COM-1600) is used to perform the potentiometric titration with a potassium hydroxide solution of 0.5 mol / L (ethanol solution), with a factor (f) of 1.003 at 20 ° C, the end point is set at the point of maximum slope of the titration curve (titration volume = B (ml), KOH solution titer = f), The same procedure is carried out on a blank sample (titration volume = C (ml)), and the acid number is calculated by the following equation, solid acid number (mgKOH / g) = {(B-C) * 0.5 * 56.11 * f} / A / solid component,

wherein, in the above formulas, "X" represents an ether oxygen atom, a sulfur sulfur atom, or an amine nitrogen atom; R1 and R2 each represent a hydrogen atom or a C1 to C10 alkyl group; R3 and R5 each represent a C1 to C20 alkyl, cycloalkyl or aryl group; Y R4 and R6 each represent a C1 to C10 alkylene group. 2. Resin composition according to claim 1, wherein the acid-reactive compound is at least one compound represented by the following formula (31), (32) or (33),

wherein, in the above formulas, "X" represents an ether oxygen atom, a sulfur sulfur atom, or an amine nitrogen atom; R7 represents a hydrogen atom or a C1 to C9 alkyl group; R8 represents a hydrogen atom or a C1 to C10 alkyl group; R9 and R11 each represent a C1 to C20 alkyl, cycloalkyl or aryl group; R10 represents a single bond or a C1 to C9 alkylene group; and R12 represents a C1 to C9 alkylene group. 3. Resin composition according to claim 1 or 2, wherein the polymer (A) comprises a structural unit derived from a monomer having the structure represented by the following formula (1),

wherein, in the above formula (1), "X" represents an ether oxygen atom, a sulfur sulfur atom or an amine nitrogen atom; R1 and R2 each represent a hydrogen atom or a C1 to C10 alkyl group; R3 represents a C1 to C20 alkyl, cycloalkyl or aryl group; and the total number of carbon atoms in R1, R2, and R3 is 4 or more. Resin composition according to any one of claims 1 to 3, in which the polymer (A) comprises a structural unit derived from a monomer having the structure represented by the following formula (1),

wherein, in the above formula (1), "X" represents an ether oxygen atom, a sulfur sulfur atom or an amine nitrogen atom; R1 and R2 each represent a hydrogen atom or a C1 to C10 alkyl group; R3 represents a C1 to C20 alkyl, cycloalkyl or aryl group; and the total number of carbon atoms in R1, R2, and R3 is 8 or more. Resin composition according to any one of claims 1 to 4, in which the polymer (A) further comprises a structural unit derived from a (meth) acrylate monomer containing an oxyethylene group represented by the following formula ( 2-1), Z1- (CH2CH2O) nR21 ■■■ (2-1) wherein, in the formula, Z1 represents an acryloyloxy or methacryloyloxy group; R21 represents a hydrogen atom or a C1 to C10 alkyl or aryl group; and "n" is an integer from 1 to 15. Resin composition according to any one of claims 1 to 5, in which the weight average molecular weight determined by gel permeation chromatography using polystyrene as standard resin of the polymer (A) is 2,000 to 19,000, the content of the polymer (A) is at least 57% by mass of the total mass of the resin composition, and the viscosity at 25 ° C determined using a Brookfield viscometer is less than 2,000 mPas. Resin composition according to any one of claims 1 to 6, in which the weight average molecular weight determined by gel permeation chromatography using polystyrene as standard resin of the polymer (A) is 3,000 to 16,000, the content of the polymer (A) is at least 59% by mass of the total mass of the resin composition, and the viscosity determined in the same way as above is less than 1,000 mPas. 8. Antifouling coating composition, comprising: a resin composition according to any one of claims 1 to 7; Y an antifouling agent. An antifouling coating composition according to claim 8, comprising at least one antifouling agent selected from cuprous oxide, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, and medetomidine. An antifouling coating composition according to claim 8 or 9, wherein the content of a volatile organic compound is 410 g / l or less; the content of a volatile organic compound is defined as: content of a volatile organic compound (g / l) = specific gravity of the ^{composition x1000x (100-non-volatile content) /} 100 in which the non-volatile content is determined according to the following procedure: In an aluminum dish, 0.50 grams of a sample (antifouling coating composition) is weighed and 3 ml of toluene is added using a dropper to spread the sample evenly over the bottom of the dish in order to preliminarily dry the sample in a water bath of 70 to 80 ° C, then final drying of the sample is carried out for 2 hours using a hot air blower at 105 ° C, The non-volatile content is calculated from the mass of the sample before preliminary drying (mass before drying) and the mass after final drying (mass after drying) using the following equation. non-volatile content (% by mass) = mass after removal / mass before drying x100 An antifouling coating composition according to any one of claims 8 to 10, wherein the viscosity at 25 ° C determined using a Brookfield viscometer is less than 3,000 mPas. An antifouling coating composition according to any one of claims 8 to 11, wherein the change in viscosity determined using a Brookfield viscometer is 400% or less after storage at 40 ° C for 90 days. An antifouling coating composition according to any one of claims 8 to 12, further comprising a thermoplastic resin.